Process for the manufacture of rubber elastic threads of sulfochlorinated polyolefins



United States Patent F Int. Cl. D01d 7/04: 5/06; D01f 7/00 U.S. Cl.264-183 6 Claims ABSTRACT on THE DISCLOSURE In the process formanufacturing rubber-elastic threads of sulfochlorinated polyolefins theimprovement comprising shaping a diamine-free solution ofsulfochlorinated polyethylene, sulfochlorinated polypropylene or asulfochlorinated olefin copolymer to form threads in the presence of o-,m-, and p-phenylene diamine, 4,4'-diaminobenzophenone, xylylene diamine,diamino decane, 2,2- diamino-diethyl ether, N,N-dimethyl-ethylenediamine, ethylene diamine, 1,3-propylene-diamine or 1,6-diam'inohexane.

The present invention relates to a process for the manufacture ofrubber-elastic threads of sulfochlorinated polyolefins.

It is known that the sulfochlorination of polyolefins yields productshaving good elastic properties.

It is further known to add vulcanization agents to solutions ofsulfochlorinated ethylene/propylene copolymers, to spin these solutionsand then to vulcanize the threads. The elastic threads obtained in thismanner possess almost the same mechanical properties as those possessedby threads made of natural rubber or other types of synthetic rubber. Asvulcanization agents which may be add ed to the spinning solution, thereare known metal oxides (monoor multivalent), monoor polyamines and saltsof an alkali metal or alkaline earth metal of weak, nonvolatile acids.

These vulcanization agents, however, have the grave drawback that theyare either insoluble in the spinning solution such as, for example, themetal oxides and may, therefore, lead to incrustations of the sp'inneretor, as do the polyamines, they interlace the sulfochlorinatedpolyolefins already prior to the spinning process owing to their verygood reactivity, which process the polyolefins gelatinize or precipitateand also incrust the spinneret. It is, furthermore, difficult to obtainfrom such solutions threads having a fine titer as required in theprocess of covering the threads for the manufacture of rubber-elasticwoven, knitted, Raschel or plaited articles, for example fabrics forcorsets and bodices as well as bathing suits and the like.

Now we have found that substantially improved, rubber-elastic threadscan be obtained by spinning the sulfochlorinated polyolefins from theirdiamine-free solutions, in the presence of diamines to produceinterlacing.

The spinning process can be carried out in apparatuses that aregenerally used, for example in a suitable dry spinning apparatus, or itcan be carried out especially advantageously in an apparatus workingaccording to the wet spinning process. In this case the diamine is addedto the coagulation bath.

The sulfochlorinated polyolefins used may be sulfochlorinatedhomopolyolefins, such as sulfochlorinated ice polyethylene as described,for example, in French Patent 1,167,042, or-sulfochlorinatedpolypropylene as described, for example, in German Patent 1,015,603, butpreferably sulfochlorinated olefin copolymers as described, for example,in Austrian Patent 203,709.

For the preparation of the spinning solution all solvents may be usedwhich are inert towards diamines and whichare not too difiicultlyvolatile. In the preferred wet spinning process the solvents must,moreover, be miscible with the liquid in the coagulation bath.

Examples of suitable solvents are aromatic hydrocarbons, such as benzeneor toluene, aliphatic hydrocarbons such as, for example, gasoline havinga boiling point of to C., or halogenated hydrocarbons, such aschloro-benzene, chloroform, carbon tetrachloride being especiallyadvantageous since the polyolefin for sulfochlorination is dissolvedtherein. However, mixtures of solvents may also be used. For thepreparation of the solutions the comminuted polymer is advantageouslystirred in a closed vessel with the calculated amount of solvent at aroom temperature until it is completely dissolved. However, -it is alsopossible to employ the polymer solution directly after thesulfochlorination (and after having blown out the gases which are stilldissolved therein). Depending on the molecular weight at the polymerused, solutions of 5 to 25 percent strength are spun. The viscoussolutions obtained are water-clear and colorless. The viscosity of thespinning solution is determined by the falling ball test usuallyemployed in the viscose industry. With the use of steel balls (DINspecification 5401, diameter 2.5 mm.; type :5, S.K.F.), the period offall of the ball, at 20 C. and for a height of fall of 20 cm., shall bewithin the range of from 10 to 400 seconds, preferably within the rangeof from 20 to 100 seconds. In order to control the degree ofpolymerization, the relative or reduced viscosity of a solution of 1percent strength of the polymer in carbon tetrachloride is determined at20 C. The spinning solution may be spun not only through spinnerets ofnoble metal but also through glass spinnerets.

Depending on the required titer of the thread, the number of openingsmay vary from 5 to openings, and the diameter of the opening may varyfrom 30 to 600 The diamines having an interlacing action may be primaryor secondary aromatic, araliphat'ic or aliphatic diamines, the latterbeing used With special advantage. The carbon chain of the diamines mayalso be interrupted by bridging members, for example by ether-oxygen orcarbonyl groups. There are mentioned for example, the phenylenediamines, 4,4'-diaminobenzophenone, xylylene diamine, the diaminodecanes, the 2,2'-diamino-diethyl ether, N,N-dimethyl-ethylene diamine.Diamines having a chain of 2 to 6 carbon atoms, such as ethylenediamine, 1,3-propylene-diamine or 1,6-diamino-hexane are used withspecial advantage.

For the coagulation bath of the preferred wet spinning process there maybe used as liquid for the coagulation bath short chain alcohols, such asmethanol, ethanol, propanol, isopropanol, or low-molecular weightketones, such as acetone or mixtures thereof. The diamines having aninterlacing action are added to this coagulation bath.

To the diamine-containing coagulation bath there may be added substancesbinding hydrochloric acid, for example tertiary amines as trimethylamine, triethyl amine or sodium bicarbonate to bind the hydrochloricacid forming between the polyolefin sulfochloride and the diamine in themodified Schotten-Baumann reaction.

The rubber-elastic threads obtained by the process claimed have a hightensile strength (0.5 to 0.7 gram/ denier). In addition to coarsethreads there may also be spun threads having a titer below 1 denier.

The threads have an excellent resistance against the action of light,heat and ozone. Thus the threads do not exhibit any impairment of theirproperties after having been subjected to a treatment in hot air at 100C. for a period of more than 24 hours. A measurable deterioration of theproperty of the thread does not occur even if the threads are heated forshort periods to 190 C. The threads Withstand storage well; they do notyellow nor do they age; moreover, they are entirely odorless.

Owing to these properties, which are not possessed by natural rubber anddiiferent types of synthetic rubber, the novel rubber-elastic threadsconstitute an important advance in the art.

The novel threads may be processed advantageously not only in the barestate, but also in the covered state. Their use is not limited to thefield of fine textiles such as, for example, fabrics for bodices, butthey may be employed advantageously for industrial uses.

The following examples serve to illustrate the invention, but they arenot intended to limit it thereto, the parts being by weight:

EXAMPLE 1 A solution of 5.8 parts of a sulfochlorinated ethylene/propylene copolymer with 35 mole percent of propylene (reduced viscosity3.1, measured in a solution of 1% strength in xylene, at 25 C.)containing 2.2% by weight of sulfur and 21.7% by weight of chlorine, in94.2 parts of carbon tetrachloride was spun through a spinneret of goldand platinum having 30 openings of a diameter of 80 each into a mixtureof 95 parts of methanol and parts of ethylene diamine. The coagulationbath flowed at a rate of liters/hour in countercurrent to the thread.According to the falling ball test (steel balls having a diameter of 2.5mm.), the viscosity of the spinning solu tion at C. corresponded to atime of fall of the ball of 40 seconds. The portion of the coagulationbath through which the thread had to pass had a length of 100 cm. Thespinning solution was expressed from an autoclave under a pressure of1.9 atmospheres of nitrogen over a spinning arc into the coagulationbath which had a temperature of 16 C. and was then drawn otf viathree-roller-systems at a rate of 2.28 meters per minute. The time ofstay of the thread in the coagulation bath was 26.3 seconds. Thecoagulated thread bundle was then washed in a bath having a length of110 cm. and containing water of a temperature of 45 C., and wound upwhile it was drawn in a ratio of 1:1.5. At an elongation of 300%, thedried thread had a tensile strength of 0.54 gram/denier, an initialmodulus of 0.078 gram/ denier and a yield stress (in tension) of 0.019gram/ denier.

On analysis of the thread material there were found: 2.1% by Weight S,0.90% by weight N, 20.1% by Weight Cl, which corresponds to thequantitative conversion of all existing sulfochloride groups withethylene diamine.

EXAMPLE 2 A thread spun under the same conditions as those described inExample 1 was fixed in a drying cabinet with circulating air at 190 C.for seconds while being drawn -by 100%. At an elongation of 300%, thethread treated in this manner had a tensile strength of 0.72gram/denier.

EXAMPLE 3 A solution of 8.0 parts of a sulfochlorinated ethylene/propylene copolymer with mole percent of propylene (reduced viscosity3.10, measured in a solution of 1% strength in xylene, at 25 C.) with2.2% by weight of sulfur and 21.7% by weight of chlorine in 92 parts ofchloroform was spun through a spinneret of gold and platinum (number ofopenings: 20, diameter of the opening: 200 into a mixture comprising 94parts of methanol, 5 parts of ethylene diamine and 1 part of triethylamine. The coagulation bath flowed at a rate of 20 liters/ hour incountercurrent to the thread. The viscosity of the spinning solutionamounted to 129 falling ball seconds at 20 C. The portion of thecoagulation bath through which the thread had to pass had a length of 95cm. The spinning solution was expressed into the coagulation bath undera pressure of 2.8 atmospheres of nitrogen. The thread was drawn off at arate of 3.53 meters/minute. The c0 agulated and washed thread bundle waswound up at a rate of 4.73 meters/minute, and dried. The spinning threadwas then either placed for 10 minutes in an acetic anhydride bath havinga temperature of 30 to 50 C., washed on being withdrawn from the bathand dried, or it was allowed, after having been spun and dried in adesiccator, to stand over acetic anhydride at 20 C. for 24 hours. At anelongation of 211%, the thread prepared in this manner had a tensilestrength of 0.4 gram/denier, an initial modulus of 0.05 gram/denier anda yield stress (in tension) of 0.02 gram/ denier.

A thread having equally good elastic properties was obtained on using,instead of the polymer employed above, a sulfochlorinatedethylene/propylene copolymer having a content of C hydrocarbons of 30mole percent, an 1 value of 3.9 (measured as described above), a sulfurcontent of 1.1% and a chlorine content of 17.3%.

When carrying out the process according to the invention, it is quitegenerally advantageous to subject the spun thread to a subsequent heattreatment at temperaures wihin the range of from to 200 C. This heattreatment may be carried out directly after the spinning process, or itmay be carried out during or after th following washing process andduring the drawing process. Owing to this heat treatment, theinterlacing reaction is terminated and the surplus diamine removed,however, above all the strength of the thread is improved thereby.

It is advantageous, moreover, to treat the thread, after it has left thecoagulation bath and after it has been washed, with a compound having anacylating action, such as acetic anhydride, to acylate free aminogroups. This after-treatment prevents yellowing of the threads.

We claim:

1. In a wet spinning process for the manufacture of rubber-like elasticthreads of sulfochlorinated polyolefins, the improvement comprisingspinning a diamine-free solution of sulfochlorinated polyethylene,sulfochlorinated polypropylene or a sulfochlorinated olefin copolymerinto a spinning bath consisting of methanol, ethanol, propanol,isopropanol or acetone which contains o-, m-, and p-phenylene diamine,4,4-diaminobenzophenone, xylylene diamine, diamino decane,2,2'-diamino-diethyl ether, N,N-dimethyl-ethy1ene diamine, ethylenediamine, 1,3- propylene-diamine or 1,6-diamino-hexane.

2. In a wet spinning process for the manufacture of rubber-like elasticthreads of sulfochlorinated polyolefins, the improvement comprisingspinning a diamine-free solution of sulfochlorinated polyethylene,sulfochlorinated polypropylene or a sulfochlorinated olefin copolymerinto a spinning bath consisting of methanol, ethanol, propanol,isopropanol or acetone which contains o, m-, and p-phenylene diamine,4,4'-diaminobenzophenone, xylylene diamine, diamino decane,2,2'-diamino-diethyl ether, N,N'-dimethyl-ethylene diamine, ethylenediamine, 1,3- propylene-diamine or 1,6-diamino-hexane, and an acidbinding substance selected from the group consisting of tertiary aminesand sodium bicarbonate.

3. In the process for manufacturing rubber-elastic threads ofsulfochlorinated polyolefins the improvement comprising spinning adiamine-free solution of sulfochlorinated polyethylene, sulfochlorinatedpolypropylene or a sulfochlorinated olefin copolymer to form threads andcontacting said threads with a member selected from the group consistingof o-, m-, and p-phenylene diamine, 4,4'-diaminobenzophenone, xylylenediamine, diamino decane, 2,2-diamino-diethyl ether,N,N'-dimethyl-ethylene diamine, ethylene diamine, 1,3-propylene-diamineor l,6-diamino-hexane.

4,. In the process for manufacturing rubber-elastic threads ofsulfochlorinated polyolefins the improvement comprising spinning adiamine-free solution of sulfochlorinated polyethylene, sulfochlorinatedpolypropylene or a sulfochlorinated olefin copolymer to form threads,contacting the threads with a member selected from the group consisiingof 0-, m-, and p-phenylene diamino, 4,4- diaminobenzophenone, xylylenediamine, diamino decane, 2,2'-di-amino-diethyl ether,N,N'-dimethyl-ethylene diamine, ethylene diamine, 1,3-propylene-diamineor 1,6- diamino-hexane, and subjecting the undrawn threads to asubsequent heat treatment at 70 to 200 C.

5. In the process for manufacturing rubber-elastic threads ofsulfochlorinated polyolefins the improvement comprising spinning adiamine-free solution of sulfochlorinated polyethylene, sulfochlorinatedpolypropylene or a sulfochlorinated olefin copolymer to form threads,contacting the threads with a member selected from the group consistingof 0-, m-, and p-phenylene diamine, 4,4- diaminobenzophenone, Xylylenediamine, diamino decane, 2,2-diamino-diethyl ether, N,N'-dimethyl-ethylene diamine, ethylene diamine, 1,3-propylene-diamine or1,6- diamino-hexane, drawing the threads and subjecting the drawnthreads to a subsequent heat treatment at 70 to 200 C.

6. In the process for manufacturing rubber-elastic threads ofsulfochlorinated polyolefins the improvement comprising spinning adiamine-free solution of sulfochlorinated polyethylene, sulfochlorinatedpolypropylene or a sulfochlorinated olefin copolymer to form threads,contacting the threads with a member selected from the group consistingof o-, m-, and p-phenylene diamine, 4,4- diaminobenzophenone, xylylenediamine, diamino decane, 2,2'-diamino-diethyl ether,N.N'-dimethyl-ethylene diamine, ethylene diamine, 1,3-propylene-diamineor 1,6- diamino-hexane, and subjecting the threads to a treatment withacylating agents.

References Cited UNITED STATES PATENTS 2,416,060 2/1947 McAlevy et al.260-79.3 X 2,416,061 2/ 1947 McAlevy et al.

2,586,363 2/1957 McAlevy et al. 26079.3 2,955,017 10/1960 Boyer 264183 X2,961,290 11/1960 Kolb 264-184 3,001,965 9/1961 Kalil 260--79.3 X3,079,218 2/1963 Gialio et al.

3,198,868 8/1965 Pedretti et al. 264347 3,326,884 6/ 1967 King.

3,324,088 6/1967 Waldron 26079.3 3,405,204 10/ 1968 McCormack 26483FOREIGN PATENTS 246,565 1/1961 Australia.

JULIUS FROME, Primary Examiner J. H. WOO, Assistant Examiner US. Cl.X.R. 264184, 236, 347

